WO2006099392A2 - Fonctionnalisation induite par micro-ondes de nanotubes de carbone a paroi unique et composites prepares au moyen de celle-ci - Google Patents

Fonctionnalisation induite par micro-ondes de nanotubes de carbone a paroi unique et composites prepares au moyen de celle-ci Download PDF

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WO2006099392A2
WO2006099392A2 PCT/US2006/009067 US2006009067W WO2006099392A2 WO 2006099392 A2 WO2006099392 A2 WO 2006099392A2 US 2006009067 W US2006009067 W US 2006009067W WO 2006099392 A2 WO2006099392 A2 WO 2006099392A2
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nanomaterial
reaction
swnts
composite
microwave
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Somenath Mitra
Zafar Iqbal
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New Jersey Institute Of Technology
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Definitions

  • the present invention relates to the field of nanomaterials, including single wall nanotubes (SWNTs), multiwall nanotubes, nanohorns, fullerenes, nano onions, and nanocomposites. More particularly, the present invention relates to a method of forming, producing or manufacturing functionalized nanomaterials, and, specifically, soluble nanomaterials.
  • the presently described invention also relates to nanomaterial-based composites consisting of a target material, which can include ceramic, polymer, or metallic matrices incorporated into nanomaterials, as well as a method or synthesis technique for the formation, production, or manufacture of nanocarbon composites through microwave- induced reaction.
  • SWNTs Single wall carbon nanotubes
  • An SWNT comprises a single hexagonal layer of carbon atoms (a graphene sheet) that has been rolled up to form a seamless cylinder.
  • Three types of SWNTs with differing chirality are expected to open new frontiers with applications ranging from new materials, to electronics and molecular scale sensing.
  • Several processes for large scale synthesis/manufacture of SWNTs are also being developed by various research groups around the globe.
  • CVD methods include high pressure and catalytic CVD.
  • SWNTs produced from different methods show slight variations in their electronic properties, and in size distribution (Kuzmany et al., Synthetic Metals, 141 (2004) 113-122). (All references cited in this paragraph are herein incorporated by reference in their entirety).
  • SWNTs Functionaiization of SWNTs has been of much interest to the scientific community because it enhances applicability. For example, insoluble SWNTs can be rendered soluble, which will lead to easy processibility, as working with a suspension is always a challenge. Functionaiization may also lead to more efficient purification/separation techniques, such as, those based on chirality, or, the separation of metallic SWNTs from semi-conducting ones. More importantly, functionaiization leads to the development of new classes of material with specificity for different physical and chemical properties.
  • SWNTs have no functional groups and are consequently quite inert. Limited reactivity arises due to the curvature induced stress from the non-planer sp 2 carbons and the misaligned ⁇ orbitals. While there is a wealth of literature on the derivatization of the SWNTs, the two most general approaches appear to be 1, 3-dipolar cycloaddition, and oxidation of some of the atoms at the tube ends or on the tube wall, and then substitution of the functionality thus formed (-F, - OH, -COOH). At this point, a variety of synthetic organic reactions can be carried out. An example of the former approach is a reaction with azomethine.
  • Acid treatment has been the most commonly used functionalization approach. It leads to debundling of the nanotubes, and is the first step towards amidation, esterification and other applications.
  • Conventional acid treatment is a long process, however, as it requires several hours to several days depending upon the requirements of the final product. Further, most of the reported methods also involve multiple steps, and only a limited solubility has been achieved (order of few milligrams per liter) (see for example, Loupy A. Solvent-free microwave organic synthesis as an efficient procedure for green chemistry, C. R. Chimie (2004) 7(2) : 103-112; Lewis et al., Accelerated imidization reactions using microwave radiation, J. Polym. Sci. A (1992) 30: 1647-1653).
  • the development of a fast, efficient and controllable technique for SWNT functionalization will dramatically speed-up their real world applications.
  • Microwaves are electromagnetic radiation in the 0.3-300 GHz frequency range (corresponding to 0.1-100 cm wavelength). To avoid interference with communication networks, all microwave heaters (domestic or scientific) are designed to work at either 2.45 GHz or 0.9 GHz, of which, the former is more prevalent. According to Planck's law, the energy at this wavelength is 0.3 cal/mol, and is therefore insufficient for molecular excitation, thus most of the energy is used in substrate heat-up.
  • the mechanism of microwave heating is different from that of conventional heating, where heat is transferred by conduction, convection or radiation. In microwave heating, electromagnetic energy is transformed into heat through ionic conduction and the friction due to rapid reorientation of the dipoles under microwave radiation. The larger the dipole moment of a molecule, the more vigorous is the oscillation in the microwave field, consequently more heating. This type of heating is fast, has no inertia, and is in-situ without heating the surroundings.
  • SWNTs single wall carbon nanotubes
  • stiffness, elasticity and high Young's modulus make them ideal candidates for structural reinforcements in the fabrication of high strength, light weight, and high performance composites.
  • the excellent mechanical, thermal and electrical properties of carbon nanotubes and SWNTs would be significantly enhanced by the development of nanocomposites containing ceramic, polymer and metal incorporated into carbon nanotubes.
  • Desirable properties for ceramic, polymer and metal composites include mechanical toughness, wear resistance, and the reduction in crack growth coupled with improved thermal conductivity, resistance to thermal shock and increased electrical conductance.
  • the ceramics are inherently brittle and the incorporation of SWNTs is known to have improved toughness by as much as 24% (Kamalakaran et al., Microstructural characterization of C-SiC- carbon nanotube composite flakes, Carbon (2004) 42(1): 1-4).
  • Fabrication methods such as, hot pressing, sintering, milling, covalent grafting and in-situ catalytic growth in ceramic and polymer matrices via chemical vapor deposition (CVD), have been used. These methods may be classified as those where the carbon nanotubes and the ceramic were physically mixed and then bonded by heat-treatment, or those where the nanotubes were grown in a ceramic matrix via CVD. This typically generates a mixture of single and multiwall nanotubes along with amorphous carbon.
  • CVD chemical vapor deposition
  • AI 2 O 3 /nanotube composites were prepared by ball milling a methanol suspension of the ceramic and nanotubes for 24 hours (Wang et al., Contact-damage-resistant ceramic/single-wall carbon nanotubes and ceramic/graphic composites, Nature Materials (2004) 3: 539-544).
  • An example of the latter is the synthesis from a slurry of SiC and ferrocene in xylene, which was sprayed into a reactor at 1000 0 C under argon (Kamalakaran et al.).
  • the present invention is directed to a method for rapidly functionalizing a nanomaterial, comprising performing a functionalization reaction wherein said functionalization reaction comprises subjecting said nanomaterial and at least one functionalizing reactant to microwave conditions.
  • the invention is further directed to a method for rapidly generating a soluble, functionalized nanomaterial comprising a functionalization reaction wherein said functionalization reaction comprises subjecting said non nanomaterial and at least one functionalizing reactant to microwave conditions.
  • the invention is also directed to a method for producing a nanomaterial composite comprising the step of growing a ceramic on a nanomaterial.
  • the invention is even further directed to a method for producing a nanomaterial composite comprising the step of growing or polymerizing target material precursors on the nanomaterial.
  • the invention additionally is directed to a method for synthesizing a nanomaterial composite comprising: providing a nanomaterial; adding a target material selected from the group consisting of a ceramic compound, a metal, a polymer, and combinations thereof, to said nanomaterial, wherein the target material and nanomaterial combination is exposed to microwave conditions to form said nanomaterial composite.
  • the invention is finally directed to a method for synthesizing a nanomaterial composite comprising of decomposing a metal salt or an organometallic compound on the nanomaterial.
  • Figure 1 compares the FTIR spectra of (a) pristine SWNTs, (b) HNO 3 treated SWNTs with microwave, and (c) 2, 6-dinitroaniline functionalized SWNTs.
  • Figure 2 compares the Raman spectra of (a) pristine SWNTs and (b) 2, 6- dinitroanaline functionalized SWNTs.
  • Figure 3 compares the FTIR spectra of (a) L-methionene, (b) salicylaldehyde, and (c) final product of 1, 3-dipolar cycloaddition of SWNTs.
  • Figure 4 (a) shows the UV-vis absorption spectroscopy of the mixture of starting material.
  • Figure 4 (b) shows the UV-vis absorption spectroscopy of the final product of 1, 3-dipolar cycloaddition of SWNTs
  • Figure 5 presents the H NMR of the final product of 1, 3-dipolar cycloaddition of SWNTs
  • Figure 6 sets forth SEM images of (a) pristine SWNTs; (b) same pristine SWNTs at higher magnification; (c) SWNTs after 1, 3-dipolar cycloaddition functionalizaton; and (d) same SWNTs after 1, 3-dipolar cycloaddition functionalizaton at higher magnification.
  • Figure 7 consists of a series of photographs of SWNTs solution in distilled water as follows: (a) 0.05mg/ml, (b) 0.1 mg/ml, (c) 0.2 mg/ml, (d) 0.3 mg/ml, (e) 0.5 mg/ml and (f) 2mg/ml.
  • Figure 9 depicts FTIR spectra (excited by 632.8 nm radiation) of the functionalized SWNTs, wherein (a) pristine SWNTs; and (b) microwave functionalized SWNTs.
  • Figure 9 depicts Raman spectra (excited by 632.8 nm radiation) of the functionalized SWNTs wherein (a) pristine SWNTs; (b) functionalized SWNTs in solid phase, and (c) functionalized SWNTs in aqueous solution.
  • Figure 10 depicts visible-near infrared (vis-NIR) spectra data under pure nitrogen at a heating rate of lOoC per minute for pristine and microwave functionalized SWNTs, wherein (a) Pristine SWNTs suspended in dimethyformamide, and (b) Aqueous solution of microwave reacted nanotubes.
  • vis-NIR visible-near infrared
  • FIG. 10 depicts thermogravimetric analysis (TGA) data under pure nitrogen at a heating rate of lOoC per minute for pristine and microwave functionalized SWNTs, wherein (c) pristine SWNT powder and (d) microwave functionalized SWNTs.
  • TGA thermogravimetric analysis
  • Figure 11 comprises optical images of the SWNTs and SiC composite rapidly precipitating out of the fine suspension.
  • Figure 11 (a) depicts the whole composite at a scale bar of 1 cm.
  • Figure 11 (b) is a magnified portion of the composite shown at a scale bar of 2mm.
  • Figure 12 shows an X-ray diffraction (XRD) pattern of the face-centered cubic structure of the SiC component in the SiC-SWNT composite.
  • Figure 13 shows FTIR spectra of the materials in the reaction process used to create the composite at various stages of the process.
  • Figure 13 (a) depicts the purified and acid washed SWNTs.
  • Figure 13 (b) depicts starting material of chlorotrimethyl silane.
  • Figure 13 (c) depicts the SWNTs-SiC composite.
  • the "*" in figures 13 (a) and 13 (c) denotes the water impurity from KBr used as a supporting matrix for the samples.
  • Figure 14 depicts the Raman spectra of the SWNT composites in a pristine form and as-reacted with SiC.
  • Figure 14 (a) depicts the spectrum of pristine SWNTs, while Figure 14 (b) depicts the spectrum of the SiC-SWNT composite.
  • Figure 15 depicts SEM and TEM images of the SWNTs-SiC composite.
  • Figure 15 (a) depicts the SEM image of SWNTs covered by fine SiC particles at a scale bar of 200 nm.
  • Figure 15 (b) depicts a SEM image showing an individual nanotube covered by SiC particles at a scale bar of 200 nm.
  • Figure 15 (c) depicts a SEM image showing a portion of SWNTs fully covered by SiC spheres at a scale bar of 200 nm.
  • Figure 15 (d) depicts a SEM image showing embedded nanotubes from the fractured composite at a scale bar of 1 ⁇ m.
  • Figure 15 (e) depicts a TEM image of debundled, SiC coated SWIMTs, and randomly linked by SiC spheres at a scale bar of 50 nm.
  • Figure 15 (f) depicts a magnified TEM image showing the SiC coated and linked nanotubes at a scale bar of 10 nm.
  • Figure 16 (a) depicts the mechanism for growth of the SiC-SWNT composite.
  • Figure 16 (b) is a pictorial illustration of the linkage between SiC and SWNTs.
  • Figure 17 depicts carbon nanotubes coated by solid phase LiAIH 4 decomposition.
  • Figure 18 depicts the energy dispersive x-ray (EDX) spectra of carbon nanotubes coated with LiAIH 4 decomposition.
  • the present invention is a method of forming, producing or manufacturing rapidly functionalized and highly soluble nanomaterials, most specifically carbon nanotubes. Specifically, we present the first application of microwave-induced functionalization of Single wall nanotubes (SWNTs), which reduces the reaction time to the order of minutes.
  • SWNTs Single wall nanotubes
  • nanomaterials can include single wall nanotubes (SWNTs), multiwall nanotubes, nanohorns, fullerenes, nano onions and nanocomposites. These nanomaterial also include but are not limited to carbon based nanomaterial such as carbon nanotubes and carbon SWNTs.
  • Functionalization of nanomaterials serves several important functions. Materials such as carbon nanotubes are inert and do not mix and blend easily in most matrices. They are not soluble either, so they can not be processed easily either in thin films or polymer composites. Functionalization allows the chemical structure of the nanotubes to be modified, and other functional groups, polymers, ceramics, biological molecules such as enzymes and other appropriate chemical moeties can be attached. For example treating with acid generates -COOH groups to which other functionalities can be attached by a variety of chemical reactions.
  • Some functionalization reactions may be carboxylation, sulfonation, esterification, thiolation, carbine addition, nitration, nucleophylic cyclopropanation, bromination, fluorination, diels alder reaction, amidation, cycloaddition, polymerization, adsorption of polymers, addition of biological molecules and enzymes etc.
  • the funtionalization may be covalent bonding to the nanotube, or noncovalent adsorption or wrapping.
  • the nanotubes may be rendered soluble in aqueous, organic, polar, nonpolar, hydrogen bonding, ionic liquids, and other solvents so that they can be processed easily.
  • Polymer or ceramic precursor may also be reacted with nanotubes to form composites, or biological molecules may be attached for drug delivery, sensing or other important functions.
  • the process of the invention begins with the combining of the desired nanomaterial, either prefunctionalized or non-functionalized, with the functionalizing reactant such as an acid, base, urea, alcohol, organic solvent, benzene, acetone and any other reactant that achieves the desired functionalization reaction.
  • the combination is then subjected to appropriate microwave conditions that result in functionalization of the nanomaterial.
  • the functionalized nanomaterial can be subjected to further functionalization reactions using the same inventive process. For example, it may be necessary to functionalize a nanomaterial with carboxyl groups prior to functionalizing with desired functionalizing reactant.
  • the method of the invention incorporates the use of microwave induced functionalization of SWNTs.
  • This high-energy procedure to reduce the reaction time to the order of minutes.
  • the microwave provides in-situ, molecular heating in a microwave oven.
  • the power and time can be adjusted for optimized performance and results.
  • the microwave power is adjustable anywhere from a few hundred watts to several kilowatts depending upon how quickly one desires the reaction to be completed. Such conditions will vary depending upon the desired functionalization reaction.
  • Preferred reaction times for functionalization are anywhere from 1 second to 30 minutes.
  • the amount of material to be processed can range anywhere from a few mg to several kg,..
  • Two preferred embodiments include amidation of SWNTs and 1, 3-dipolar cycloaddition of SWNTs.
  • the amidation reaction is completed in two steps (as opposed to three in conventional approaches). Specifically, while the step involving acyl chlorination is bypassed, the yield remains the same.
  • the 1, 3- dipolar cycloaddtion of SWNTs embodiment can be carried out in , for example, 15 minutes under microwave conditions, and the results are similar to what was achieved in 5 days using conventional methods.
  • microwave assisted reactions are a fast and effective method for reactions involving SWNTs.
  • the first preferred embodiment involves carboxylation (generation of -COOH) of SWNTs followed by amidation, as shown in the scheme 1 below.
  • the second preferred embodiment is 1, 3-dipolar cycloaddtion reaction of
  • a distinct advantage of the present invention is rapid funtionalization.
  • the speed of this reaction is partially due to rapid heating and even superheating at a molecular level. Side reactions are also eliminated as the bulk does not need to be heated.
  • the microwave induced reaction occurs in a matter of seconds or minutes and can generate a high purity product with high yield. This is advantageous because it makes the overall process cost effective.
  • the microwave induced reactions as a means of nanotube functionalization is also extremely important from the stand point of process development and scale-up.
  • the ease of creating functionalized soluble nanomaterials increases production of nanomaterials at a reduced price thereby enabling sufficient quantities to be produced for use in commercial goods as well as production at a cost that can be tolerated by consumer markets. Additionally the method in generally reduces reaction time by orders of magnitude and provides high yield adding to its cost effectiveness.
  • Carbon nanotubes for example, have inert, graphitic sidewalls and are therefore extremely insoluble in common solvents.
  • a new method to produce highly effective and rapid sidewall functionalization was required and is presently disclosed.
  • One embodiment of the present invention is a method for generating soluble nanomaterials by the use of microwaves and an acidic environment.
  • the acidic environment can be a suspension of nanotubes in an acid or acid mixture.
  • a blend of acids in a variety of proportions can be used to create the acidic environment.
  • some examples of acids that could be utilized to create the acidic environment include, nitric acid, sulfuric acid, hydrochloric acid, as well as other organic and inorganic acids.
  • a pairing of nitric acid and sulfuric acid can be used to create the acid treatment.
  • a 1: 1 mixture of concentrated nitric acid and sulfuric acid in water was used.
  • This embodiment is an environmentally friendly, microwave-induced method to prepare highly water-soluble single-walled nanotubes (SWNTs) in about three minutes, using a closed vessel reactor.
  • This embodiment has generated measured solubilities of more than 10 mg of nanotubes per milliliter of water and ethanol, which is several orders of magnitude higher than what has previously been achieved in the art. Additionally the solutions were free of suspended nanotubes as determined by light scattering measurements, and for the first time Raman spectrum of SWNTs was obtained from its solution phase.
  • highly pure single wall carbon nanotubes were suspended in a 1: 1 mixture of concentrated nitric acid and sulfuric acid in water and reacted in a closed vessel microwave oven for less than five minutes.
  • the placing of a nanomaterial in an acidic environment maybe called an acid treatment.
  • the nanotubes when the nanotubes contact the acid treatment, the nanotubes became nitrated.
  • the presently described method offers the significant advantages of generating high solubility functionalized nanomaterials that are rapidly functionalized at low temperatures with preferred alignment in solution and electrically conductive properties. Additionally, the method itself is environmentally friendly and scalable for industry thereby enabling the production of economical bulk quantities of highly reproducible product to consumers.
  • the method of the present disclosure offers significant advantages relative to prior art.
  • the advantageous properties and/or characteristics of the disclosed method include, but are not limited to, high solubility functionalized nanomaterials, preferred alignment of the nanomaterials in solution, rapidly functionalized nanomaterials, electrically conducting nanomaterials, environmentally friendly, scalable for industry to produce bulk quantities and economically bring the product to consumers, it generates highly reproducible products and can operate at low temperatures.
  • the resultant high water and alcohol solubility of the method of the invention will enable nanomaterials and SWNTs to be more easily processed in operations involving chemical reactions, physical blending, or thin film formation. Further, the nanomaterials and SWNT will have a more preferable alignment during deposition from solution due to the presently disclosed method. The enhanced alignment will facilitate the creation of novel nanoelectronic device architectures.
  • the resulting soluble nanomaterials of the invention can also be electrically conducting.
  • the SWNT can display significantly higher conductivity in de-ionized water, for example, in this case as high as 215.8 ⁇ S (one or two orders of magnitude higher is also possible) relative to that of 1.5 ⁇ S for de-ionized water. This advantage raises the possibility for electrical manipulation (such as, electrodeposition) of the SWNTs from a solution phase.
  • the presently disclosed method of synthesis is also highly reproducible as evidenced by the creation of a solid composite of similar morphology, shape, and color with every reaction (see Example 3).
  • the high level of reproducibility is partially due to the controlled environment. This is advantageous because high purity products can be obtained.
  • the presently disclosed method of synthesis is appealing because it requires a relatively low temperature microwave-induced reaction to produce soluble nanomaterials.
  • the presently disclosed method of synthesis has the ability to operate at a low temperature due in part to in-situ heating at the reaction site. This is advantageous because it leads to fast reaction kinetics and reactions that would not otherwise be possible.
  • the present invention is also directed to a composite consisting of target material(s) such as ceramic, polymer or metals to be incorporated into or grown on nanomaterials such as carbon nanotubes or SWNTs.
  • target material(s) such as ceramic, polymer or metals
  • the present invention provides a technique for the formation, production, or manufacture of nanomaterial composites through a controllable, rapid, relatively low temperature microwave-induced reaction.
  • the process of the invention comprises the combination of a target material precursor with the desired nanomaterial under microwave conditions such that the target material forms on the nanomaterial (e.g. polymerization).
  • appropriate quantities of the target material and the nanomaterial are blended or mixed together under known conditions and are then subjected to appropriate microwave conditions to form the desired composite.
  • a precursor to the target material is combined with the nanomaterial under known conditions, and said combination is subjected to appropriate microwave conditions that induce formation of the target material from the precursor which then combines with the nanomaterial to form the desired composite. More specifically, a reaction can be carried out to deposit ceramic or polymer material on the nanotube.
  • a reaction can be carried out to deposit ceramic or polymer material on the nanotube.
  • polymer or ceramic precursors can be polymerized or synthesized directly on the nanotube sidewalls.
  • the functionalization of the nanomaterial be accomplished using the method of this invention prior to subjecting the nanomaterial to the composite formation set forth in the invention.
  • Ceramic compounds that are suitable for use in the invention include, but are not limited to, carbides, borides, nitrides, suicides, barium titanate, bismuth strontium calcium copper oxide, boron carbide, boron nitride, aluminum silicates, earthenware, Ferrite, lead zirconate titanate, magnesium diboride, porcelain, silicon carbide, silicon nitride, Steatite, uranium oxide, yttrium barium copper oxide, zinc oxide, zirconia, and combinations thereof.
  • metals suitable for use in the invention include salt such as UAIH4. UBH4; and CdS.
  • preferred polymers include, but are not limited to methyl methacrylate, polyvinyl pyrrolidone, polyurethane, polyamide and any other related polymers.
  • the process of the invention is excellent for creating novel nanoscale silicon carbide (SiC)-carbon nanotube composites and metal-nanotube composites.
  • the present invention relates to a method enabling the formation of a ceramic or polymer directly on the carbon nanotubes, rather than physical mixing, or the growth of nanotubes in a ceramic or polymer matrix.
  • the described technique creates mechanical toughness, wear resistance, and the reduction in crack growth coupled with improved thermal conductivity, resistance to thermal shock and increased electrical conductance.
  • the process is excellent for using a variety of silanol compounds, including silicon carbide (SiC), to create novel nanoscale composites such as silicon carbide (SiC)-carbon nanotubes, and, more generally, metal-nanotube composites.
  • SiC silicon carbide
  • SiC is an interesting material because it can be used for high-temperature and high-power electronic applications due to its excellent properties, such as high mechanical strength, high thermal stability, high thermal conductivity and large band gap.
  • nanometer size SiC nanostructure might hold novel chemical and physical properties for fabricating electronic nanodevices.
  • a preferred embodiment includes a novel, low temperature, microwave-induced approach for the synthesis of a high purity SiC-SWNT composite.
  • the reaction of the invention can be completed in a matter of minutes, and involves the nucleation of SiC directly on the SWNT bundles.
  • formation of multiwalled tubes and other carbonaceous structures is usually performed in the reverse of what occurs in the present invention, i.e. growth of SWNTs in a ceramic matrix does not occur in the process of the invention because the process begins with the use of highly purified SWNTs.
  • the reaction involves the pyrolysis of the chlorotrimethylsilane and simultaneous nucleation of nanoscale SiC spheres onto carbon nanotubes. This reaction was carried out in microwave, and the whole process involves one step and about 10 min.
  • An alternative embodiment of the invention relates to the synthesis of a ceramic carbon nanotube composite which incorporates ceramic matrices into carbon nanotubes.
  • One specific embodiment of the invention is a ceramic SWNT composite, which incorporates ceramic matrices into SWNTs. Examples of these embodiments are illustrated in Figures 12 - 15.
  • the present invention includes but is not limited to nanotubes, nanohoms, graphite and all similar or related structures.
  • a preferred embodiment involves utilizing a microwave oven and a reaction chamber, lined with Teflon PFA® and fitted with a pressure controller.
  • the SWNTs are first treated with a solution having acidic properties, such as nitric acid, sulfuric acid, and any other suitable organic and inorganic acid, for a short period of time under microwave conditions to reduce or eliminate residual metal catalyst and generate carboxyl groups.
  • a silinol or a polymer precursor compound e.g., methyl methacrylate
  • pretreated SWNTs and the precursor compound are added to the microwave reaction vessel and subjected to microwave induced reaction while controlling time, power (wattage) and pressure.
  • the silanol precursor decomposes and the polymer precursor polymerizes to form said compound.
  • the liquid in the control vessel is cooled and is then removed from the reaction chamber, washed and then dried.
  • the method of synthesis of the ceramic SWNTs presently described preferably involves the utilization of a microwave oven and a Teflon PFA® lined reaction chamber fitted with a pressure controller.
  • the SWNTs are treated in the microwave with a nitric acid solution.
  • the pretreated SWNTs are then added, along with chlorotrimethylsilane to the microwave reaction vessel and subjected to microwave induced reaction while controlling time, power (wattage) and pressure, thereby synthesizing the ceramic SWNT composites presently disclosed (see Example 3 for more detail).
  • the composite has been grown on the nanotubes by decomposing a chemical.
  • the reaction involves the microwave-induced decomposition of chlorotrimethylsilane in the presence of carbon nanotubes.
  • Chlorotrimethylsilane provides an easy to decompose source of silicon for in-situ forming of the SiC component of the composite.
  • the reaction involves the microwave-induced decomposition of a precursor chemical in the presence of carbon nanotubes, such that the new formed nanocarbon composite is formed directly around the tube.
  • interfacial bonding is improved by in-situ growth of the ceramic or polymer or metal on the carbon nanotubes as opposed to the methods described in the prior art whereby the interfacial bonding occurs by adding the carbon nanotubes onto a pre-prepared ceramic or polymer.
  • the presently disclosed composite formed in accordance with the disclosed method of a controllable rapid, relatively low temperature microwave-induced interfacial bonding significantly increases the mechanical toughness, wear resistance, thermal conductivity, resistance to thermal shock, and electrical conductance while reducing crack growth.
  • the nanotube-metal composites can be fabricated by reactive processes. Reaction with a metal salt or a complex can be carried out.
  • Reaction with a metal salt or a complex can be carried out.
  • an example is the reaction with lithium aluminum hydride (LJAIH4).
  • LJAIH4 lithium aluminum hydride
  • the solid phase reaction of the nanotubes and UAIH4 was carried out in an oven at temperature 25O 0 C or for a few minutes in a microwave.
  • the ceramic element can be substituted for by a polymer thereby creating a polymer nanomaterial composite or a metal thereby creating a metal nanomaterial composite.
  • the composites of the present invention offer significant advantages relative to prior art.
  • the advantageous properties and/or characteristics of the disclosed composite include, but are not limited to, mechanical toughness, wear resistance, reduction in crack growth, improved thermal conductivity and resistance to thermal shock, and electrical conductance.
  • mechanical toughness ceramics, for example are inherently brittle and the incorporation of nanotubes is reported to have improved toughness by as much as 24%.
  • An increase in the mechanical toughness is a direct result of the improvement of the interfacial bonding caused by the in-situ growth of the ceramic or polymer on the carbon nanotubes as opposed to the prior art whereby the carbon nanotubes is merely added onto the pre-prepared ceramic.
  • One benefit of mechanical toughness is that it allows the carbon nanotubes to be used under more strenuous conditions.
  • Wear resistance is much like mechanical toughness and is attributable to the improved interfacial bonding caused by the in-situ growth of the ceramic on the carbon nanotubes rather than merely by adding the carbon nanotubes onto the pre-prepared ceramic, thereby extending the life of the carbon nanotubes in a variety of applications.
  • the method of synthesis of the invention further facilitates a reduction in crack growth which can be attributed to the high binding capabilities of the carbon nanotubes.
  • the method of synthesis of the composite of the present invention offers significant advantages relative to prior art.
  • the advantageous properties and/or characteristics of the disclosed method of synthesis of the composite includes, but are not limited to, rapid, low temperature microwave-induced reaction to create a novel nanoscale silicon carbide (SiC)-SWNT composite without side reactions.
  • the method is highly reproducible by creating a solid composite of similar morphology, shape, color was obtained every time, cost effective and environmentally safe. Additionally, the speed of the reaction can be controlled. Finally, the in-situ heating facilitates reactions that are otherwise not possible.
  • the speed of the reaction is partially due to rapid heating and even superheating at a molecular level. Side reactions are also eliminated as the bulk does not need to be heated.
  • the microwave induced reaction occurs in a matter of seconds or minutes and can generate a high purity product with high yield. This is advantageous because it makes the overall process cost effective.
  • the method uses a relatively low temperature microwave-induced reaction to create the novel composites, it is advantageous because it leads to fast reaction kinetics and reactions that would not otherwise be possible. Also, the high level of reproducibility offered by the invention is advantageous because high purity products can be obtained. Of course, the presently disclosed method of synthesis is cost effective as it reduces reaction time by orders of magnitude and provides high yield. Finally, the invention has great appeal due to it being environmentally safe (minimal requirement of energy and chemicals).
  • the first step was the generation of carboxylic acid groups on the SWNTS.
  • 6 ⁇ 10 mg of pristine SWNTs from Hipco process was loaded into an extraction vessel, along with 20 ml of cone. HNO 3 (70%).
  • the microwave power setting was 75% (total of 900 watts), the pressure was set at 125 PSI, and the reaction was carried out for 10 ⁇ 15 min. After cooling the vessel to room temperature, the reacted mixture was filtered, washed and dried. About 5 mg of this carboxylic acid grafted SWNTs was used to react with 2, 6-dinitroaniline.
  • the organic phase was washed with water for 5 times, and then dried with Na2SO4 over night. Then, it was evaporated, washed with ethyl ether, and around 7 mg of dark brown solid was obtained after evaporation.
  • the solid was evaluated using FTIR, H-NMR, SEM, and UV spectroscopy.
  • the conventional approach to amidation for SWNTs involves carboxylation, acyl chlorination, and amidation. It involves three steps and typical reaction time is of 3 to 5 days.
  • the amidation of SWNTS in a microwave was a two steps process, and it's total reaction time is about 20 to 30 min.
  • SWNTs functionalized through amidation in microwave were characterized using FTIR and Raman spectroscopy. The results are presented in figure 1 and 2 respectively.
  • FIG. 1 shows the FTIR spectra of pristine SWNT (a), HNO 3 treated SWNT (b), and finally after 2, 6-dinitroaniline functionalized SWNT (c).
  • the band at 1626 cm “1 is water impurity from KBr used for making the pellet, and this peak existed in figure Ib and Ic as well.
  • the C O band at 1730 cm "1 in the HNO3 treated SWNT indicated successful generation of COOH on the nanotubes (figure Ib).
  • the sharp peak at 1384 cm “1 is probably due to the nitration of NO 2 in SWNTs, which occurred during the high pressure HNO 3 treatment in microwave.
  • the Raman measurements were carried out using a Horiba/Jobin Yvon LabRaman system place with 632.8 nm excitation.
  • the Raman spectroscopy was carried out on both pristine and functionalized SWNTs.
  • the Raman spectrum of functionalized SWNTs shows significant fluorescence, due to the coverage of the amine on wall or the ends of SWNTs. Similar observation was also reported by several different groups (Huang et al., Nano. Lett, (2002) 2, 311; Lin et al., J. Phys Chem. B (2002), 106, 1294-1298; Ya-Ping et al., Ace. Chem. Res. (2002), 35, 1096-1104).
  • the enhanced peak at about 1330 cm-1 was attributed to covalent modification, as it revealed sp 3 -hybridization of disorder within the nanotube framework.
  • the functionalized SWNTs shows the absence of the aldehyde C-H stretching peaks at 2749 cm “1 and 2845 cm “1 , which were present in the original aldehyde (figure 3b).
  • the aldehyde group was expected to be gone after functionalization. Therefore the missing of the aldehyde C-H peaks in figure 3c implies successful reaction of the functionalization.
  • the aromatic C-H stretching band in figure 3c at 3052 cm “1 was slightly shifted, as compare to spectra 3b of the aldehyde, which was at 3060 cm “1 .
  • the peaks at 2917 cm “1 and 2849 cm “1 were from the attached amino acid.
  • UV-vis absorption analysis presented in figure 4 provided further evidence of the functionalization reaction.
  • the UV-vis absorption measurements were made in CHCI 3 .
  • Spectra (a) is from the mixture of the starting material taken in the same ratio as the reaction. It showed two broad absorption bands at about 250 and 330 nm. After the reaction, two bands remained, but shifted to the left, which was in agreement with the observation of Prato et al (Prato et al., J. Am. Chem. Soc. (2002) 124, 760-761). The shift of absorption bands provided further proof of a change in molecular structure brought by reaction.
  • SWNTs SEM image of purified SWNTs and 1, 3-dipolar cycloaddition functionalized SWNTs are presented in figure 6.
  • the pristine SWNTs exist as bundles with 20 to 30 nm size in diameter, as shown in figure 6(a) and 6(b).
  • the walls of the tube were clean and smooth.
  • SWNTs tended to aggregate into bigger bundles after the reaction, with typical diameter of 200 to 300 nm. These are shown in the spectra of 6(c) and 6(d). Because of the attachment of amino acid and aldehyde, the wall the tube became rough as shown in figure 6(d). However, the cylindrical shape of SWNTs is clearly observable after functionalization.
  • This exemplary embodiment shows a method of synthesis of highly, water and alcohol, soluble nanotubes, and in particular, SWNT.
  • the experiment includes utilizing a CEM Model 205 microwave oven with a typically 100 ml or larger closed vessel reaction chamber, lined with Teflon PFA® and fitted with a 0 ⁇ 200 psi pressure controller.
  • the SWNTs used were prepared by the high pressure HiPCO process.
  • SWNTs deposited from aqueous solution generate scanning electron microscope (SEM) and transmission electron microscope (TEM) images displayed in Figures 8A and 8B, respectively.
  • SEM images indicate clear alignment of the depositing nanotubes resulting from capillary forces during evaporation of the solvating water molecules. Alignment of the carbon nanotubes is seen each time after evaporation of a drop of the solution.
  • the TEM image shows extensive debundling of the SWNT ropes, but no indication of structural modification of the sidewalls can be seen at this magnification level.
  • the strong line observed at 1355 cm “1 was assigned to the asymmetric S02 stretching mode of the acid sulfonate (-SO 2 OH) group, whereas the lower frequency line at 1200 cm “1 was assigned to the SO 2 symmetric stretching mode.
  • the shoulder near 2600 cm “1 was assigned to the - OH group of the sulfonic acid group.
  • the FTIR spectrum is consistent with elemental analysis of the functionalized SWNTs, which showed that one in three carbon atom on the SWNT backbone was carboxylated, and one in ten was sulfonated.
  • SWNTs of three different diameters are indicated by the peaks at 189 cm “1 , 213 cm “1 and 252 cm “1 due to the SWNT radial breathing modes (RBMs).
  • the strong tangential C-C mode is seen at 1578 cm “1 , and a weak line due to defects and disorder on the SWNT framework is observed at 1299 cm “1 .
  • RBMs SWNT radial breathing modes
  • Figure 9Bc shows the Raman spectrum of the functionalized SWNTs in aqueous solution - the first time such a spectrum has been obtained for SWNTs. Probably because of water solvation around the nanotube backbone, RBM modes are not observed and the tangential mode frequency is shifted up in value by 15 cm "1 relative to that of the functionalized solid.
  • the degree of nitration and carboxylation of the SWNT structure indicated by the infrared and Raman data was quantified by thermogravimetric analysis (TGA) measurements on pristine and microwave functionalized SWNTs performed under dry nitrogen at a heating rate of lOoC per minute from 3Oo to 500oC.
  • TGA traces shown in Figure 4B indicate that compared to pristine SWNTs, the functionalized SWNT lose about 50% of its weight due to dissociation of the -NO 2 and -COOH groups from the nanotube backbone and tube ends. This would indicate that approximately every four carbons on the SWNT structure is functionalized by the microwave process.
  • aqueous solutions of microwave functionalized SWNTs are electrically conducting, with conductivity in de-ionized water of 215.8 ⁇ S relative to that of 1.5 ⁇ S for de-ionized water. This raises the possibility for electrical manipulation (such as, electrodeposition) of the SWNTs from a solution phase.
  • This exemplary embodiment shows a method of synthesis of ceramic-SWNT composite.
  • the experiment includes utilizing a CEM Model 205 microwave oven with a typically 100 ml or larger reaction chamber, lined with Teflon PFA® and fitted with a 0 ⁇ 200 psi pressure controller.
  • the Fourier transform infrared spectroscopy (FTIR) measurements were made either in highly purified KBr pellets (solid sample), or on NaCI crystal window (liquid sample) using a Perkin Elmer instrument.
  • the Raman spectra were obtained using a Renishaw System 1000 Micro-Raman Spectrometer with 785nm laser as the excitation source.
  • the transmission electron microscope (TEM) images were recorded using a TOPCON 20OkV Ultra-High Resolution Transmission Electron Microscope.
  • SEM scanning electron microscope
  • EDX energy dispersive X-ray
  • XRD Thin film X-ray diffraction
  • the SWNTs were first treated in nitric acid solution for few minutes under microwave radiation.
  • about 10 mg of the pretreated SWNTs and 5 ml of chlorotrimethylsilane were added to the microwave reaction vessel.
  • another 5 ml of chlorotrimethylsilane was used as the control in a separate vessel.
  • Both the vessels were subjected to microwave induced reaction for 10 minutes, with the power set at 75% of a total of 900 watts, and the pressure set at 125 psi. Once cooled, the liquid in the control vessel remained clear, but a tree-like solid composite was observed standing in the reaction solution.
  • EDX analysis detected four elements in the composite: C, Si, O and Cl, with atomic compositions of 55%, 33%, 9%, and 3% respectively. This indicated a o composite composition of 65% of SiC, 15% of SWNTs and 15% of SiO 2 by weight, assuming that all the oxygen was incorporated in SiO 2 . The relatively small amount of chlorine might have been absorbed from the chlorotrimethylsilane that remained after washing and drying.
  • nanocrystalline SiC is clearly indicated by the XRD pattern displayed in Figure 12, which shows broadened (111), (220) and (311) reflections of face-centered-cubic SiC at 2 ⁇ values of 35.6, 60.2 and 71.7 degrees, respectively.
  • the presence of o amorphous SiO 2 is indicated by a broad shoulder at a 26 value near 22 degrees.
  • the FTIR spectra of the starting material, the final composite and the chlorotrimethylsilane in the control vessel are shown in Figure 13. Without the SWNTs, the chlorotrimethylsilane in the control vessel remained unchanged under microwave irradiation, and its spectrum was identical to that of the starting 5 material, which is shown in Figure 13b.
  • the FTIR spectrum from the nitric acid purified SWNTs is shown in Figure 13a.
  • the SEM images in Figure 15 provide insights into how the three dimensional architecture of the composite was formed.
  • the nucleation of SiC probably occurred on the SWNT sidewalls at the onset of the reaction.
  • the SiC particles randomly cross-linked as evident from Figure 15a and grew into the macroscopic architecture shown in Figure 11.
  • the SWNTs were completely covered by the SiC spheres.
  • the image shown in Figure 15d is from the surface of a fractured region, and the nanotubes that formed the underlying framework of the composite structure are still embedded. This indicates strong interfacial binding of the SWNTs to the SiC particles.
  • the nanotubes therefore appear to reinforce the composite in a manner similar to steel in reinforced concrete. It is likely that the high tensile strength of the SWNTs prevented their breakage during fracture of the composite.
  • FIG. 16a A proposed mechanism for the growth of the SiC-SWNT composite is shown in Figure 16a.
  • the growth appeared to be initiated by the reaction of -Si(CH 3 ) 3 at the -COOH sites by forming HCI and CO 2 .
  • the methyl-silane thus formed was further decomposed by the microwave radiation to produce randomly growing SiC nanoparticles, which covered the nanotube surface and led to the formation of a heterogeneous SiC-SWNT network.
  • the process depicted in Figure 16b shows a layer of SiC chemically bonded to the SWNT surface, onto which larger SiC spheres grew.
  • the oxygen in the reaction chamber reacted to form small amounts of SiO 2 , which can be etched away by dilute HF.
  • the embodiment of the invention as synthesized through the synthesis method of the present invention is a high purity SiC-SWNT composite synthesized through a novel, low temperature, microwave-induced approach as verified by the illustrated infrared and Raman spectroscopy, x-ray diffraction, and electron microscopy data.
  • the synthesis reaction which was completed in a matter of minutes, involved the nucleation of SiC directly on the SWNT bundles. Formation of multiwalled nanotubes and other carbonaceous structures usually seen in the reverse approach of growing SWNTs in a ceramic matrix were not observed.

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Abstract

L'invention concerne un procédé permettant de former, de produire ou de fabriquer des nanomatériaux fonctionnalisés et, plus précisément, des nanomatériaux fonctionnalisés solubles. L'invention concerne également des composites à base de nanomatériaux comprenant un matériau cible pouvant renfermer des matrices céramiques, polymères ou métalliques incorporées dans les nanomatériaux ou développées sur ceux-ci, ainsi qu'un procédé ou technique de synthèse destiné à la formation, production ou fabrication de composites à base de nanomatériaux par réaction induite par micro-ondes.
PCT/US2006/009067 2005-03-11 2006-03-13 Fonctionnalisation induite par micro-ondes de nanotubes de carbone a paroi unique et composites prepares au moyen de celle-ci WO2006099392A2 (fr)

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US8182783B2 (en) 2006-11-16 2012-05-22 New Jersey Institute Of Technology Rapid microwave process for purification of nanocarbon preparations
US8317978B1 (en) * 2010-04-07 2012-11-27 Manning Thelma G Nitriding of carbon nanotubes

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Publication number Priority date Publication date Assignee Title
US20090304923A1 (en) * 2005-03-11 2009-12-10 New Jersey Institute Of Technology Microwave Synthesis of Metal-Carbon Nanotube Composites
US9169579B2 (en) * 2005-03-11 2015-10-27 New Jersey Institute Of Technology Carbon nanotube mediated membrane extraction
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US8758717B2 (en) * 2006-10-19 2014-06-24 Rensselaer Polytechnic Institute Electrical current-induced structural changes and chemical functionalization of carbon nanotubes
US20080131658A1 (en) * 2006-12-05 2008-06-05 Vijay Wakharkar Electronic packages and components thereof formed by co-deposited carbon nanotubes
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JP5364978B2 (ja) * 2007-03-28 2013-12-11 富士通セミコンダクター株式会社 表面改質カーボンナノチューブ系材料、その製造方法、電子部材および電子装置
JP2009084090A (ja) * 2007-09-28 2009-04-23 Fujifilm Corp 表面修飾カーボン材料およびその製造方法
KR100907334B1 (ko) * 2008-01-04 2009-07-13 성균관대학교산학협력단 알루미늄과 탄소재료 간의 공유결합을 형성하는 방법, 알루미늄과 탄소재료 복합체를 제조하는 방법 및 그 방법에 의하여 제조된 알루미늄과 탄소재료 복합체
US9039900B2 (en) * 2008-05-09 2015-05-26 New Jersey Institute Of Technology Membrane distillation apparatus and methods
US9643165B2 (en) * 2008-06-18 2017-05-09 Board Of Trustees Of The University Of Arkansas Doped-carbon composites, synthesizing methods and applications of the same
KR20100026432A (ko) * 2008-08-29 2010-03-10 삼성전자주식회사 탄소나노튜브 플레이트 제조 방법
US8435931B2 (en) * 2009-07-17 2013-05-07 Exxonmobil Research And Engineering Company Reduced friction lubricating oils containing functionalized carbon nanomaterials
US8841454B2 (en) * 2009-07-17 2014-09-23 Exxonmobil Research And Engineering Company Functionalized carbon nanostructures which are soluble in hydrocarbons and method for preparation
WO2011014476A1 (fr) * 2009-07-30 2011-02-03 Ut-Battelle, Llc Pastille composite de combustible nucléaire
CN102574688A (zh) 2009-07-31 2012-07-11 麻省理工学院 涉及形成碳基纳米管的系统和方法
WO2011051223A1 (fr) * 2009-10-28 2011-05-05 Futurecarbon Gmbh Procédé de production de nanomatériaux carbonés et/ou micromatériaux carbonés et matériau correspondant
WO2011066288A2 (fr) * 2009-11-25 2011-06-03 Massachusetts Institute Of Technology Systèmes et procédés d'amélioration de la croissance de nanostructures à base de carbone
US9273398B2 (en) 2010-01-16 2016-03-01 Nanoridge Materials, Inc. Metallized nanotubes
US8225704B2 (en) 2010-01-16 2012-07-24 Nanoridge Materials, Inc. Armor with transformed nanotube material
US20110177322A1 (en) * 2010-01-16 2011-07-21 Douglas Charles Ogrin Ceramic articles and methods
CN102373505A (zh) * 2010-08-17 2012-03-14 深圳大学 碳化硅纳米线的微波制备方法
US8778226B2 (en) 2010-09-30 2014-07-15 Ut-Battelle, Llc Luminescent systems based on the isolation of conjugated PI systems and edge charge compensation with polar molecules on a charged nanostructured surface
US9663368B2 (en) 2010-10-28 2017-05-30 Massachusetts Institute Of Technology Carbon-based nanostructure formation using large scale active growth structures
US8487017B2 (en) 2011-06-27 2013-07-16 Covidien Lp Biodegradable materials for orthopedic devices based on polymer stereocomplexes
KR101356792B1 (ko) * 2012-07-04 2014-01-28 한국과학기술원 그래핀-탄소나노튜브의 계층적 구조체 및 그의 제조 방법
EP2961535B1 (fr) 2013-02-28 2018-01-17 N12 Technologies, Inc. Distribution à base de cartouche de film de nanostructure
KR102437634B1 (ko) 2013-12-26 2022-08-26 텍사스 테크 유니버시티 시스템 융합 필라멘트 제작된 부품의 향상된 비드간 확산성 결합을 위한 ｃｎｔ 충전 중합체 복합물의 마이크로파-유도 국부적 가열
US9765455B2 (en) 2014-01-31 2017-09-19 United Technologies Corporation Method of desizing fiber
CN105131321A (zh) 2014-06-04 2015-12-09 苏州高通新材料科技有限公司 用酸处理有机高分子材料的方法，以及表面附碳材料、含有官能化石墨烯的粉末产品
CN106146756B (zh) * 2016-06-29 2018-11-16 常州轻工职业技术学院 一种石墨烯接枝聚烯烃的方法
CN108423670A (zh) * 2018-03-30 2018-08-21 深圳烯湾科技有限公司 石墨烯的表面修饰方法
KR20200010806A (ko) 2018-07-23 2020-01-31 삼성전자주식회사 연마 슬러리 및 그 제조 방법과 반도체 소자의 제조 방법
KR102653892B1 (ko) 2018-08-30 2024-04-02 삼성전자주식회사 화학적 기계적 연마용 슬러리 조성물, 그의 제조 방법, 및 그를 이용한 반도체 소자의 제조 방법
US11234298B2 (en) 2018-11-15 2022-01-25 Whirlpool Corporation Hybrid nanoreinforced liner for microwave oven
KR20200109549A (ko) 2019-03-13 2020-09-23 삼성전자주식회사 연마 슬러리 및 반도체 소자의 제조 방법
CN110562983B (zh) * 2019-09-04 2023-12-01 哈尔滨工业大学（威海） 高性能吸波材料的高效制备装置及制备方法
CN115445637A (zh) * 2022-09-02 2022-12-09 中南民族大学 一种镉/硫化镉异质结及其制备方法和在可见光光催化分解水产氢中的应用

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860565A (en) * 1973-10-01 1975-01-14 Minnesota Mining & Mfg Encapsulated isocyanurate catalyst
US5576358A (en) * 1995-02-03 1996-11-19 Alliedsignal Inc. Composition for use in friction materials and articles formed therefrom
US5653775A (en) * 1996-01-26 1997-08-05 Minnesota Mining And Manufacturing Company Microwave sintering of sol-gel derived abrasive grain
US5770018A (en) * 1996-04-10 1998-06-23 Valence Technology, Inc. Method for preparing lithium manganese oxide compounds
US6832735B2 (en) * 2002-01-03 2004-12-21 Nanoproducts Corporation Post-processed nanoscale powders and method for such post-processing
ATE276388T1 (de) * 1996-09-17 2004-10-15 Hyperion Catalysis Int Plasma behandelte kohlenstoffibrillen und herstellungsverfahren
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
US5980699A (en) * 1997-10-24 1999-11-09 Southwest Research Institute Method for preparing silicon nitride and silicon nitride composites
US6232264B1 (en) * 1998-06-18 2001-05-15 Vanderbilt University Polymetallic precursors and compositions and methods for making supported polymetallic nanocomposites
JP2001254103A (ja) * 2000-03-13 2001-09-18 Sanei Kasei Kk ナノコンポジット構造を有する金属粒子及び自己組織化によるその製造方法
EP1444701A4 (fr) * 2001-07-27 2005-01-12 Eikos Inc Revetements conformes contenant des nanotubes de carbone
US7147712B2 (en) * 2001-10-02 2006-12-12 Invitrogen Corporation Method of semiconductor nanoparticle synthesis
US20040029706A1 (en) * 2002-02-14 2004-02-12 Barrera Enrique V. Fabrication of reinforced composite material comprising carbon nanotubes, fullerenes, and vapor-grown carbon fibers for thermal barrier materials, structural ceramics, and multifunctional nanocomposite ceramics
US20040222080A1 (en) * 2002-12-17 2004-11-11 William Marsh Rice University Use of microwaves to crosslink carbon nanotubes to facilitate modification
TWI221344B (en) * 2003-04-10 2004-09-21 Univ Nat Central Composition of composite polymer electrolyte containing nano-tube and manufacturing method thereof
JP2007524727A (ja) * 2003-06-23 2007-08-30 ウィリアム・マーシュ・ライス・ユニバーシティ カーボンナノチューブで強化したエラストマー
US20050186378A1 (en) * 2004-02-23 2005-08-25 Bhatt Sanjiv M. Compositions comprising carbon nanotubes and articles formed therefrom
CN1953935B (zh) * 2004-05-14 2010-05-05 索尼德国有限责任公司 包括碳纳米管和金属碳酸盐的复合材料
US9169579B2 (en) 2005-03-11 2015-10-27 New Jersey Institute Of Technology Carbon nanotube mediated membrane extraction
US20090304923A1 (en) 2005-03-11 2009-12-10 New Jersey Institute Of Technology Microwave Synthesis of Metal-Carbon Nanotube Composites
WO2006099392A2 (fr) 2005-03-11 2006-09-21 New Jersey Institute Of Technology Fonctionnalisation induite par micro-ondes de nanotubes de carbone a paroi unique et composites prepares au moyen de celle-ci

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DELGADO J.L. ET AL.: 'Microwave-Assisted Sidewall Functionalization of Single-Wall Carbon Nanotubes by Diels-Alder Cycloaddition' CHEMICAL COMMUNICATIONS no. 15, 2004, pages 1734 - 1735, XP003009535 *
HOLZINGER M. ET AL.: 'Sidewall Functionalization of Carbon Nanotubes' ANGEW. CHEM. INT. ED. vol. 40, no. 21, 2001, pages 4002 - 4005, XP002231325 *
TASIS D. ET AL.: 'Soluble Carbon Nanotubes' CHEM. EUR. J. vol. 9, 2003, pages 4000 - 4008, XP008075908 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8182783B2 (en) 2006-11-16 2012-05-22 New Jersey Institute Of Technology Rapid microwave process for purification of nanocarbon preparations
EP2072635A1 (fr) * 2007-12-21 2009-06-24 Sungkyunkwan University Foundation for Corporate Collaboration Encapsulation de matériau carboné dans de l'aluminium
WO2009101635A1 (fr) * 2008-02-12 2009-08-20 Council Of Scientific & Industrial Research Composition à conductivité protonique améliorée
US8399149B2 (en) 2008-02-12 2013-03-19 Council Of Scientific And Industrial Research Composition with enhanced proton conductivity
US8317978B1 (en) * 2010-04-07 2012-11-27 Manning Thelma G Nitriding of carbon nanotubes

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